Thermoplastic resin composition

ABSTRACT

A thermoplastic resin composition improved in compatibility, molding or forming ability, melt-flow properties and mechanical properties, which comprises 100 parts by weight of a resin component containing 40 to 99 wt. % of a poly(arylene sulfide) (A) and 1 to 60 wt. % of polyamide-imide (B), and 0.01 to 10 parts by weight of a silane compound (C) containing at least one functional group selected from the group consisting of amino, ureido, epoxy, isocyanate and mercapto groups.

TECHNICAL FIELD

[0001] The present invention relates to a resin composition comprisingpoly(arylene sulfide) and a polyamide-imide, and particularly to athermoplastic resin composition improved in compatibility, molding orforming ability, melt-flow properties and mechanical properties.

BACKGROUND ART

[0002] Poly(arylene sulfides) (hereinafter abbreviated as “PASs”)represented by poly(phenylene sulfide) (hereinafter abbreviated as“PPS”) are engineering plastics excellent in heat resistance, flameretardancy, chemical resistance, dimensional stability, mechanicalproperties and the like, and widely used electric and electronic parts,precision machinery parts, automotive parts, etc. However, the PASs havea comparatively low glass transition temperature and are greatly loweredin elastic modulus in a temperature range not lower than the glasstransition temperature, so that their use has been limited inapplication fields of which high elastic modulus is required in a hightemperature not lower than 100° C.

[0003] On the other hand, polyamide-imides are engineering plasticsexcellent in heat resistance, mechanical properties, electricalproperties, chemical resistance and the like. However, most of them aredifficult to injection-mold, and they have been mainly used inapplication fields of varnishes, films and the like in the past.

[0004] Japanese Patent Application Laid-Open No. 306283/1994 disclosesthat resin compositions improved in melt moldability can be providedwithout impairing their heat resistance by blending an aromaticpolyamide-imide copolymer having a repeating units of a specificstructure with PPS. Since PAS and polyamide-imide are poor incompatibility with each other, however, it has been difficult to obtaina resin composition having sufficient mechanical properties by simplyblending them.

DISCLOSURE OF THE INVENTION

[0005] It is an object of the present invention to provide athermoplastic resin composition comprising a poly(arylene sulfide) andpolyamide-imide, improved in compatibility between both resins andhaving excellent molding or forming ability, melt-flow properties andmechanical properties.

[0006] Another object of the present invention is to provide athermoplastic resin composition by which both elastic modulus of apoly(arylene sulfide) at a high temperature and injection moldability ofpolyamide-imide are improved, and the flash length upon injectionmolding is reduced.

[0007] The present inventors have carried out an extensive investigationwith a view toward overcoming the above-described problems involved inthe prior art. As a result, it has been found that when a silanecompound having a specific functional group is added to a resincomponent comprising a PAS and polyamide-imide, compatibility betweenboth resins is markedly improved, thereby providing a thermoplasticresin composition having excellent molding or forming ability, melt-flowproperties and mechanical properties.

[0008] When the silane compound having the specific functional group isadded in the case where a fibrous or non-fibrous filler, other resinsand the like are incorporated into the resin component comprising thePAS and polyamide-imide, the compatibility of the respective componentsincluding the additive component with one another is markedly improvedto provide a thermoplastic resin excellent in various properties.

[0009] According to the thermoplastic resin compositions according tothe present invention, the elastic modulus of the PAS at a hightemperature and the injection moldability and extrudability of thepolyamide-imide are improved while making the best use of the flameretardancy, chemical resistance, dimension stability and mechanicalproperties brought about by the PAS , and the heat resistance,mechanical strength, electrical properties and chemical resistancebrought about by the polyamide-imide.

[0010] The present invention has been led to completion on the basis ofthese findings.

[0011] According to the present invention, there is thus provided athermoplastic resin composition comprising 100 parts by weight of aresin component containing 40 to 99 wt. % of a poly(arylene sulfide) (A)and 1 to 60 wt. % of polyamide-imide (B), and 0.01 to 10 parts by weightof a silane compound (C) containing at least one functional groupselected from the group consisting of amino, ureido, epoxy, isocyanateand mercapto groups.

BEST MODE FOR CARRYING OUT THE INVENTION Poly(arylene sulfide) (PAS)

[0012] The PAS useful in the practice of the present invention is anaromatic polymer having predominant repeating units of arylene sulfiderepresented by the formula [—Ar—S—] in which —Ar— means an arylenegroup. When the [—Ar—S—] is defined as 1 mole (basal mole), the PAS usedin the present invention is a polymer containing this repeating unit ina proportion of generally at least 50 mol %, preferably at least 70 mol%, more preferably at least 90 mol %.

[0013] As examples of the arylene group, may be mentioned a p-phenylenegroup, a m-phenylene group, substituted phenylene groups (thesubstituent being preferably an alkyl group having 1 to 6 carbon atomsor a phenyl group), a p,p′-diphenylene sulfone group, a p,p′-biphenylenegroup, a p,p′-diphenylenecarbonyl group and a naphthylene group. As thePAS, a polymer predominantly having only the same arylene groups maypreferably be used. However, a copolymer having two or more differentarylene groups may be used from the viewpoint of processability and heatresistance.

[0014] Among these PASs, PPS having predominant repeating units ofp-phenylene sulfide is particularly preferred because it is excellent inprocessability and industrially available with ease. Besides the PPS,poly(arylene ketone sulfides), poly(arylene ketone ketone sulfide) andthe like may be used. As specific examples of copolymers, may bementioned random or block copolymers having repeating units ofp-phenylene sulfide and repeating units of m-phenylene sulfide, randomor block copolymers having repeating units of phenylene sulfide andrepeating units of arylene ketone sulfide, random or block copolymershaving repeating units of phenylene sulfide and repeating units ofarylene ketone ketone sulfide, and random or block copolymers havingrepeating units of phenylene sulfide and repeating units of arylenesulfone sulfide. These PASs are preferably crystalline polymers. ThePASs are preferably linear, or slightly branched or crosslinked polymersfrom the viewpoints of toughness and strength.

[0015] Such a PAS can be obtained in accordance with any publicly knownprocess (for example, Japanese Patent Publication No. 33775/1988) inwhich an alkali metal sulfide and a dihalogen-substituted aromaticcompound are subjected to a polymerization reaction in a polar solvent.

[0016] As examples of the alkali metal sulfide, may be mentioned lithiumsulfide, sodium sulfide, potassium sulfide, rubidium sulfide and cesiumsulfide. Sodium sulfide formed by the reaction of NaSH and NaOH in thereaction system may also be used.

[0017] As examples of the dihalogen-substituted aromatic compound, maybe mentioned p-dichlorobenzene, m-dichloro-benzene, 2,5-dichlorotoluene,p-dibromobenzene, 2,6-dichloronaphthalene,1-methoxy-2,5-dichlorobenzene, 4,4′-dichlorobiphenyl,3,5-dichlorobenzoic acid, p,p′-dichloro-diphenyl ether,4,4′-dichlorodiphenyl sulfone, 4,4′-dichlorodiphenyl ether,4,4′-dichlorodiphenyl sulfone, 4,4′-dichlorodiphenyl sulfoxide and4,4′-dichlorodiphenyl ketone. These compounds may be used either singlyor in any combination thereof.

[0018] In order to introduce some branched or crosslinked structure intothe PAS, a small amount of a polyhalogen-substituted aromatic compoundhaving at least 3 halogen substituents per molecule may be used incombination. As preferable examples of the polyhalogen-substitutedaromatic compounds, may be mentioned trihalogen-substituted aromaticcompounds such as 1,2,3-trichloro-benzene, 1,2,3-tribromobenzene,1,2,4-trichlorobenzene, 1,2,4-tribromobenzene, 1,3,5-trichlorobenzene,1,3,5-tri-bromobenzene and 1,3-dichloro-5-bromobenzene, andalkyl-substituted derivatives thereof. These compounds may be usedeither singly or in any combination thereof. Among these,1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene and1,2,3-trichlorobenzene are preferred from the viewpoints ofprofitability, reactivity, physical properties and the like.

[0019] As the polar solvent, aprotic organic amide solvents typified byN-alkylpyrrolidones such as N-methyl-2-pyrrolidone (hereinafterabbreviated as NMP), 1,3-dialkyl-2-imidazolidinones, tetraalkylureas,and hexaalkyl-phosphoric triamides are preferred because they have highstability in the reaction system and are easy to provide ahigh-molecular weight polymer.

[0020] The PAS used in the present invention is a polymer having a meltviscosity within a range of generally from 10 to 500 Pa·s, preferablyfrom 15 to 450 Pa·s as measured at a temperature of 310° C. and a shearrate of 1200/sec. If the melt viscosity of the PAS is too low, themechanical properties of the resulting resin composition may possiblybecome insufficient. If the melt viscosity of the PAS is too high, theinjection moldability and extrudability of the resulting resincomposition may possibly become insufficient.

[0021] The PAS used in the present invention may be a polymer washedwith water after completion of the polymerization. However, as the PAS,there may be preferably used a polymer treated with an aqueous solutioncontaining an acid such as hydrochloric acid or acetic acid, or a mixedsolution of water and an organic solvent, or a polymer subjected to atreatment with a solution of a salt formed of a weak acid and a weakbase. In particular, the use of a PAS subjected to a washing treatmentuntil its pH in a mixed solution of acetone/water prepared in aproportion of 1:2 comes to exhibit 8.0 or lower permits more improvingthe melt-flow properties and mechanical properties of the resultingresin composition.

[0022] The PAS used in the present invention is desirably in the form ofparticles having an average particle size of 100 μm or greater. If theaverage particle size of the PAS is too small, the feed rate of theresulting thermoplastic resin composition is limited upon melt extrusionthrough an extruder, so that the resin composition has a possibilitythat the residence time of the resin composition in the extruder maybecome long to cause problems of deterioration of the resins, and thelike. In addition, such a too small particle size is not desirable fromthe viewpoint of production efficiency.

[0023] A blending proportion of the PAS in the resin compositionaccording to the present invention is 40 to 99 wt. %, preferably 45 to95 wt. %, more preferably 50 to 85 wt. % based on the total weight ofthe PAS and the polyamide-imide. If the blending proportion of the PASis too low, the mechanical strength of the resulting resin compositionis deteriorated, and moreover, the injection moldability andextrudability thereof become insufficient. If the blending proportion ofthe PAS is too high, not only the effect to improve elastic modulus at ahigh temperature of at least 150° C., but also the flash-inhibitingeffect becomes insufficient.

Polyamide-imide

[0024] The polyamide-imide (hereinafter may be referred to as “PAI”)useful in the practice of the present invention is generally a polymerproduced from an aromatic tricarboxylic acid anhydride and an aromaticdiamine and having a structural form alternately containing an imidegroup and an amide group.

[0025] The polyamide-imide is generally a polymer having, as a main unitstructure, a unit represented by the formula (1)

[0026] wherein Ar is a trivalent aromatic group containing at least onesix-membered carbon ring, R is a bivalent aromatic or aliphatic group,and R¹ is a hydrogen atom or an alkyl or phenyl group. A part(preferably less than 50 mol %, more preferably less than 30 mol %) ofthe imide bond in the formula (1) may remain as an amide bond.

[0027] As the polyamide-imide used in the present invention, isparticularly preferred a polymer having the repeating unit representedby the formula (1) in a proportion of 100 mol %. However, a copolymercontaining other repeating units in a proportion of preferably at most50 mol %, more preferably at most 30 mol % may also be used.

[0028] As examples of other repeating units, may be mentioned repeatingunits represented by the following formulae (2) to (4). The copolymermay contain one or more of these repeating units.

[0029] wherein Ar¹ is a bivalent aromatic or aliphatic group containingat least one six-membered carbon ring group, and R is a bivalentaromatic or aliphatic group;

[0030] wherein Ar² is a tetravalent aromatic group containing at leastone six-membered carbon ring group, and R is a bivalent aromatic oraliphatic group; and

[0031] wherein Ar² is a tetravalent aromatic group containing at leastone six-membered carbon ring group, and R is a bivalent aromatic oraliphatic group.

[0032] In the formula (1), specific examples of the trivalent aromaticgroup (Ar) include groups represented by the formulae (5) to (8):

[0033] Among these, the group of the formula (5) is preferred.

[0034] Specific examples of the bivalent aromatic or aliphatic group (R)include the formulae (9) to (35):

[0035] Among these, are preferred the groups represented by the formulae(9), (10), (11), (16), (17), (20), (23), (24), (27) and (28), and thegroups represented by the formulae (9), (10), (11), (20), (23) and (24)are particularly preferred, with the groups represented by the formulae(9), (11) and (20) being most preferred.

[0036] In the formula (2), specific examples of Ar¹ include groupsrepresented by the following formulae (36) to (41) in addition to thegroups represented by the formulae (9), (10), (16), (17), (18), (19),(29), (30) and (35):

[0037] In the formulae (3) and (4), specific examples of Ar² includegroups represented by the following formulae (42) and (43):

[0038] In the respective repeating units represented by the formulae (1)to (4), different groups respectively corresponding to Ar, Ar¹ , Ar² orR may be present in the polyamide-imide.

[0039] The polyamide-imide may be produced in accordance with a processsuch as (a) a process in which an aromatic tricarboxylic acid anhydridehalide and a diamine are reacted with each other in a solvent (an acidchloride process), (b) a process in which an aromatic tricarboxylic acidanhydride and a diamine are reacted with each other in a solvent (adirect polycondensation process), or (c) a process in which an aromatictricarboxylic acid anhydride and a diisocyanate are reacted with eachother in a solvent (an isocyanate process).

[0040] In the acid chloride process (a), at least two aromatictricarboxylic acid anhydride halides and diamines may be used. Further,a dicarboxylic acid dichloride or aromatic tetracarboxylic acidanhydride may be reacted as needed. The reaction can be conducted eitherby reacting the reactants in the presence or absence of a hydrogenhalide acceptor such as triethylamine and sodium hydroxide in a polarsolvent such as NMP or by reacting the reactants in the presence of thehydrogen halide acceptor likewise in a mixed solvent of an organicsolvent (for example, acetone) miscible at least in part with water andwater.

[0041] In the direct polycondensation process (b), at least two aromatictricarboxylic acid anhydrides and diamines may be used. Further, adicarboxylic acid or aromatic tetracarboxylic acid anhydride may bereacted as needed. The reaction can be conducted in the presence orabsence of a dehydration catalyst in a polar solvent such as NMP orwithout using any solvent.

[0042] In the isocyanate process (c), at least two aromatictricarboxylic acid anhydrides and diisocyanates may be used. Further, adicarboxylic acid or aromatic tetracarboxylic acid anhydride may bereacted as needed. The reaction can be conducted in a polar solvent suchas NMP or without using any solvent. In this process, effective meansfor efficiently conducting the reaction, controlling the structure of apolymer to be formed and modifying the molecular weight of the polymerare, for example, to conduct the reaction in a water content strictlycontrolled, to control the reaction temperature by multi stages toconduct a reaction for forming an imide group after completion of areaction for forming an amide group, to use a catalyst as needed, and toconduct the reaction under the strict control of a molar ratio of theacid anhydride compound to the carboxylic acid compound.

[0043] In each of the above-described processes, a monofunctionalcompound such as a monocarboxylic acid such as benzoic acid; an acidchloride such as benzoyl chloride; a dicarboxylic acid anhydride such assuccinic anhydride or naphthalenedicarboxylic acid anhydride; amonoisocyanate such as phenyl isocyanate; or a phenol may be used forthe purpose of modifying the molecular weight of a polymer to be formedor controlling the structure of terminals of the polymer. The polymerobtained in accordance with any one of the above-described processes maybe subjected to a heat treatment for converting the amido acid structureinto an imido ring as needed.

[0044] When the polymerization reaction is conducted in a solution, thepolyamide-imide used in the present invention is collected by treating asolution or slurry after completion of the reaction with an alcohol suchas methanol, ethanol or isopropanol; a ketone such as acetone or methylethyl ketone; an aliphatic hydrocarbon such as hexane; or an aromatichydrocarbon such as benzene or toluene to precipitate and wash a polymerformed. The polymer may be collected by directly removing the solvent byevaporation after completion of the polymerization reaction to deposit apolymer formed and then washing the polymer with the solvent describedabove. In the isocyanate process, the solvent may be concentrated tosome extend after completion of the polymerization reaction and thenremoved under reduced pressure by an extruder or the like.

[0045] The polyamide-imide used in the present invention may be apolymer produced in accordance with any process of the processes (a),(b) and (c). In the case where the resulting resin composition is usedin injection molding or extrusion, however, the polyamide-imide preparedby the isocyanate process (c) may preferably be used from the viewpointsof easy structure control and molecular weight modification of thepolymer formed. The polyamide-imide used in the present invention has areduced viscosity of generally 0.10 to 1.50 dl/g, preferably 0.12 to1.00 dl/g, more preferably 0.15 to 0.80 dl/g as determined by viscositymeasurement at 30° C. and a polymer concentration of 1 g/dl indimethylformamide.

[0046] A blending proportion of the polyamide-imide in the resincomposition is 1 to 60 wt. %, preferably 5 to 55 wt. %, more preferably15 to 50 wt. % based on the total weight of the PAS and thepolyamide-imide. If the blending proportion of the polyamide-imide istoo low, the effect to improve elastic modulus at a high temperaturebecomes insufficient. If the blending proportion of the PAS is too high,the mechanical strength of the resulting resin composition isdeteriorated, and moreover, the injection moldability and extrudabilitythereof become insufficient.

Silane Compound

[0047] The functional group-containing silane compound useful in thepractice of the present invention is a silane compound containing atleast one functional group selected from the group consisting of amino,ureido, epoxy, isocyanate and mercapto groups in its molecule. Thefunctional group-containing silane compound may be generally a silanecompound containing any one of these functional groups in its molecule.In some cases, it may be a silane compound containing two or more ofthese functional groups in its molecule. The silane compound used in thepresent invention is generally an alkoxysilane or halosilane containingsuch a functional group as described above in its molecule.

[0048] Specific examples of the functional group-containing silanecompound include amino group-containing silane compounds such asγ-aminopropyltrimethoxysilane, γ-amino-propyltriethoxysilane,γ-aminopropylmethyldimethoxysilane, γ-aminopropylethyldiethoxysilane,γ-aminopropylmethyl-diethoxysilane,N-(β-aminoethyl)-γ-aminopropyltrimethoxy-silane,N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane,γ-phenyl-γ-aminopropyltrimethoxysilane andγ-ureidopropyl-triethoxysilane; ureido group-containing silane compoundssuch as γ-ureidopropyltrimethoxysilane,γ-ureidopropyl-methyltrimethoxysilane, γ-ureidopropyltriethoxysilane,γ-ureidopropylmethyltriethoxysilane andγ(2-ureidoethyl)-aminopropyltrimethoxysilane; epoxy group-containingsilane compounds such as γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropyldimethylmethoxysilane,γ-glycidoxypropyl-triethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane andβ(3,4-epoxycyclohexyl)ethyltriethoxysilane; isocyanate group-containingsilane compounds such as γ-isocyanatopropyl-trimethoxysilane,γ-isocyanatopropylmethyldimethoxysilane,γ-isocyanatopropyltriethoxysilane,γ-isocyanatopropyl-methyldiethoxysilane,γ-isocyanatopropylethyldimethoxy-silane,γ-isocyanatopropylethyldiethoxysilane andγ-isocyanatopropyltrichlorosilane; and mercapto group-containing silanecompounds such as γ-mercaptopropyl-methyldimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropyl-methyldiethoxysilane, β-mercaptoethyltrimethoxysilane,β-mercaptoethyltriethoxysilane and β-mercaptoethyldimethoxy-silane.

[0049] These functional group-containing silane compounds are preferablyalkoxysilane compounds or halosilane compounds containing at least onefunctional group selected from the group consisting of amino, ureido,epoxy, isocyanate and mercapto groups. The functional group-containingalkoxysilane compounds are preferably functional group-substitutedalkyl-alkoxysilane compounds having a functional group-substituted alkylgroup and an alkoxy group. The functional group-substitutedalkyl-alkoxysilane compounds are preferably silane compounds in whichthe functional group-substituted alkyl group has 1 to 4 carbon atoms,and the alkoxy group has 1 to 4 carbon atoms, namely, “functionalgroup-substituted (C₁-C₄)alkyl. (C₁-C₄)alkoxysilane compounds”. Asexamples of such functional group-substituted alkyl-alkoxysilanecompounds, may be mentioned γ-aminopropyl.trialkoxysilane compounds,γ-glycidoxypropyl.trialkoxysilanes, γ-mercaptopropyl .trialkoxysilanes,γ-isocyanatopropyl. trialkoxysilanes and γ-ureidopropyl.trialkoxysilanesas those excellent in the effect of addition thereof and easy to beavailable.

[0050] These functional group-containing silane compounds may be usedeither singly or in any combination thereof. A compounding proportion ofthe functional group-containing silane compounds is 0.01 to 10 parts byweight, preferably 0.05 to 8 parts by weight, more preferably 0.1 to 5parts by weight based on 100 parts by weight of the total amount of thePAS and the polyamide-imide. If the compounding proportion of thesefunctional group-containing silane compounds is too low, the mechanicalproperty-improving effect by the addition thereof becomes little. If theproportion is too high on the other hand, the resulting resincomposition tends to generate gases in the course of molding or formingand processing, resulting in a molded or formed product liable to causevoids. In many cases, the functional group-containing silane compoundcan exhibit a sufficient effect in an amount of about 0.3 to 2 parts byweight per 100 parts by weight of the resin component. In the case wherea great amount of a filler is blended, or the like, however, it ispreferable to compound the functional group-containing silane compoundin a relatively great amount into the resin component for achievingsufficient compatibility. The functional group-containing silanecompound can exhibit its compatibility-improving effect in an amount ofgenerally about 0.1 to 2 wt. %, preferably about 0.3 to 1 wt. % based onthe total weight of the resin composition containing the resin componentand various kinds of additives.

Organic Amide Compound

[0051] When a small amount of an organic amide compound is added to thethermoplastic resin composition according to the present invention, themelt-flow properties and mechanical properties of the composition can beenhanced.

[0052] Examples of the organic amide compound include amides such asN,N-dimethylformamide and N,N-dimethyl-acetamide; N-alkylpyrrolidones orN-cycloalkylpyrrolidones such as N-methyl-2-pyrrolidone andN-cyclohexyl-2-pyrrolidone; N-alkylcaprolactams orN-cycloalkyl-caprolactams such as N-methyl-ε-caprolactam andN-cyclohexylcaprolactam; caprolactams such as ε-caprolactam;N,N-dialkylimidazolidinones such as 1,3-dimethyl-2-imidazolidinone;tetraalkylureas such as tetramethylurea; and hexaalkylphosphorictriamides such as hexamethyl-phosphoric triamide. These organic amidecompounds may be used either singly or in any combination thereof.

[0053] Among the organic amide compounds, the N-alkyl-pyrrolidones,N-cycloalkylpyrrolidones, N-alkyl-caprolactams,N-cycloalkylcaprolactams, caprolactams and N,N-dialkylimidazolidinonesare preferred, with the N-alkylpyrrolidones, caprolactams andN,N-dialkyl-imidazolidinones being particularly preferred.

[0054] The organic amide compound is compounded in a proportion ofgenerally 0.01 to 10 parts by weight, preferably 0.1 to 8 parts byweight, more preferably 0.5 to 5 parts by weight per 100 parts by weightof the total amount of the PAS and the polyamide-imide. If thecompounding proportion of the organic amide compound is too low, theeffects of improving the melt-flow properties and mechanical propertiesbecome little. If the compounding proportion is too high, the strengthof the resulting resin composition is lowered, and there is apossibility that unfavorable phenomena such as bleeding may be caused.

Other Thermoplastic Resins

[0055] Into the resin compositions according to the present invention,may be added other thermoplastic resins within limits not impeding theobjects of the present invention. The other thermoplastic resins arepreferably thermoplastic resins stable at a high temperature.

[0056] As examples of the other thermoplastic resins, may be mentionedaromatic polyesters such as polyethylene terephthalate and polybutyleneterephthalate; fluorocarbon resins such as polytetrafluoroethylene(PTFE), tetrafluoroethylene/hexafluoropropylene copolymers,tetrafluoroethylene/perfluoroalkyl vinyl ether copolymers,polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinylidenefluoride/hexafluoropropylene copolymers, propylene/tetrafluoroethylenecopolymers, vinylidene fluoride/chlorotrifluoroethylene copolymers andethylene/hexafluoropropylene copolymers; polyolefins such aspolyethylene and polypropylene; and polyacetal, polystyrene, polyamide,polycarbonate, polyphenylene ether, polyalkyl acrylate, ABS resins,polyvinyl chloride, liquid crystalline polyesters, poly(ether etherketone), poly(ether ketone), polysulfone and poly(ether sulfone).

[0057] These thermoplastic resins may be used either singly or in anycombination thereof. In many cases, however, the other thermoplasticresins are used in a small amount within limits not impeding the variousproperties of the resin composition of the PAS and the polyamide-imide.A preferable compounding proportion of the other thermoplastic resins isat most 50 parts by weight, more preferably at most 30 parts by weightper 100 parts by weight of the total amount of the PAS and thepolyamide-imide.

Filler

[0058] Into the thermoplastic resin compositions according to thepresent invention, may be compounded various kinds of fillers as needed.As examples of the fillers, may be mentioned fibrous fillers, such asinorganic fibrous materials such as glass fiber, carbon fiber, asbestosfiber, silica fiber, alumina fiber, zirconia fiber, boron nitride fiber,silicon nitride fiber, boron fiber and potassium titanate fiber(whisker); metallic fibrous materials such as stainless steel, aluminum,titanium, copper and brass; and high-melting organic fibrous materials(for example, Aramid fiber) such as polyamide, fluorocarbon resins,polyester resins and acrylic resins.

[0059] As examples of non-fibrous fillers, may be mentioned particulate,powdery or flaky fillers such as mica, silica, talc, alumina, kaolin,calcium sulfate, calcium carbonate, titanium oxide, magnetic powders(for example, ferrite), clay, glass powder, zinc oxide, nickelcarbonate, iron oxide, quartz powder, magnesium carbonate and bariumsulfate. Conductive fillers such as conductive carbon black may also beused as filler.

[0060] These fillers may be used either singly or in any combinationthereof. The fillers may be treated with greige goods orsurface-treating agents as needed. Examples of the greige goods orsurface-treating agents include functional compounds such as epoxycompounds, isocyanate compounds and titanate compounds. These compoundsmay be used for subjecting fillers to a surface treatment or collectingtreatment in advance, or added at the same time upon the preparation ofa resin composition.

[0061] In the thermoplastic resin compositions according to the presentinvention, as needed, these fillers may be compounded within a range ofgenerally 0 to 800 parts by weight, preferably 0 to 500 parts by weight,more preferably 0 to 300 parts by weight per 100 parts by weight of theresin component. The compounding proportion of the fillers variesaccording to the intended functions of the resulting thermoplastic resincomposition. When the thermoplastic resin composition is used as amagnetic material by compounding, for example, magnetic powder such asferrite therein, the magnetic powder is generally compounded in aproportion of about 100 to 800 parts by weight per 100 parts by weightof the resin component. When the thermoplastic resin composition is usedas a heat-conductive material by compounding a heat-conductive fillersuch as alumina, the filler is generally compounded in a proportion ofabout 50 to 300 parts by weight per 100 parts by weight of the resincomponent. In the case of electrically conductive carbon black, thecarbon black is generally compounded in a proportion of about 1 to 100parts by weight per 100 parts by weight of the resin component accordingto the desired volume resistivity of the resulting resin composition.

[0062] In particular, the compounding of an inorganic fibrous fillersuch as glass fiber permits the provision of a resin compositionexcellent in mechanical properties such as tensile strength, flexuralstrength, flexural modulus and maximum strain in bending. When theinorganic fibrous filler is compounded for improving these mechanicalproperties, it is compounded in a proportion of preferably 1 to 300parts by weight, more preferably 5 to 150 parts by weight, particularlypreferably 10 to 100 parts by weight per 100 parts by weight of theresin component.

[0063] The glass fiber-filled thermoplastic resin composition issuitable for use as an insulating material in a wide variety of fields.The carbon fiber-filled thermoplastic resin composition is suitable foruse as an electrically conductive material or sliding material. Thecarbon black-filled thermoplastic resin composition is suitable for useas an electrically conductive material. The Aramid fiber-, PTFE- orpotassium titanate whisker-filled thermoplastic resin composition issuitable for use as a sliding material. The alumina-filled thermoplasticresin composition is suitable for use as a heat-conductive material. Thesilica-filled thermoplastic resin composition is suitable for use as asealing material. The ferrite-filled thermoplastic resin composition issuitable for use as a magnetic material.

[0064] At least two fibrous filler, at least two non-fibrous fillers, orat least one fibrous filler and at least one non-fibrous filler may beused in combination. Further, at least one other thermoplastic resin andat least one filler (fibrous filler and/or non-fibrous filler) may alsobe used in combination. Specific examples thereof include the combineduse of at least one fibrous filler (for example, glass fiber) andelectrically conductive carbon black, and the combined use of PTFE andpotassium titanate fiber.

Other Additives

[0065] Into the resin compositions according to the present invention,may be suitably added, for example, resin-modifying agents such asethyleneglycidyl methacrylate, lubricants such as pentaerythritoltetrastearate, antioxidants, thermosetting resins, ultravioletabsorbents, nucleating agents such as boron nitride, flame retardants;colorants such as dyes and pigments, and the like as other additivesthan the above-described additives.

Thermoplastic Resin Composition

[0066] The thermoplastic resin compositions according to the presentinvention can be prepared by equipment and methods generally used in thepreparation of synthetic resin compositions. The resin composition canbe prepared in accordance with, for example, a process comprisingpremixing the individual raw components by means of a Henschel mixer ortumbler, adding a filler such as glass fiber, as needed, to furthercontinue the mixing, kneading the resultant mixture in a single-screw ortwin-screw extruder and then extruding the kneaded mixture into pelletsfor molding. There may also be used a process in which part of thenecessary components are mixed as a masterbatch, and the mixture ismixed with the remaining components, or a process in which part of rawmaterials used are ground for the purpose of enhancing thedispersibility of the individual components, thereby making the particlesizes of the components uniform, and they are mixed and melt-extruded.

[0067] The thermoplastic resin compositions according to the presentinvention can be molded or formed into sheets, films, tubes or othermolded or formed products by applying the conventional melt processingtechniques such as injection molding and extrusion to the compositions.The molded or formed products are excellent in stiffness at atemperature not lower than 150° C., flame retardancy, heat resistance,chemical resistance, dimensional stability, mechanical properties, andthe like and can be used in a wide variety of fields of which theseproperties are required.

EXAMPLES

[0068] The present invention will hereinafter be described morespecifically by the following Examples and Comparative Examples.However, the present invention is not limited to these examples only.

[0069] Incidentally, physical properties in the examples were determinedor measured in accordance with the following respective methods.

[0070] (1) Tensile Properties (Tensile Strength and Tensile Elongation):

[0071] The tensile strength and tensile elongation (tensile elongationat break) of each resin composition sample were determined underconditions of a measuring temperature of 23° C., a gauge length of 50 mmand a cross-head speed of 5 mm/min in accordance with ASTM D 638.

[0072] (2) Flexural Properties (Flexural Modulus, Flexural Strength andMaximum Strain in Bending):

[0073] The flexural modulus, flexural strength and maximum strain inbending of each resin composition sample were determined underconditions of a measuring temperature of 23° C., a distance betweensupports of 80 mm and a cross-head speed of 3.5 mm/min in accordancewith ASTM D 790. Incidentally, the flexural modulus were determined atmeasuring temperature of 23° C. and 150° C. in some cases. The measuredvalues in such a case were indicated with the temperature followedthereto.

[0074] (3) Melt Viscosity:

[0075] The melt viscosity of each resin composition sample was measuredunder conditions of a temperature of 310° C. and a shear rate of1,200/sec by means of a “Capirograph” (manufactured by Toyo SeikiSeisakusho, Ltd.).

[0076] (4) pH of PAS:

[0077] The pH of each PAS sample was measured in a 1:2 mixed solvent ofacetone and water. More specifically, 50 ml of acetone were added to 20g of the polymer to vigorously mix them. After 100 ml of ion-exchangedwater were further added to shake the resulting mixture for 30 minutesby a shaker, 60 ml of a supernatant liquid was taken out to measure a pHthereof.

[0078] (5) Extrudability:

[0079] Whether extrudability was good or poor was judged from the stateof extrusion upon melting and kneading each resin composition sample ina twin-screw extruder 45 mm in diameter in accordance with the followingstandard:

[0080] Good: The resin composition can be fed without hindrance;

[0081] Poor: Bite into the screws is poor, so that bridging

[0082] occurs in a feed opening, thereby causing a

[0083] scatter of extrusion rate.

[0084] (6) Evaluation Method of Flash Length:

[0085] A pellet-like extrudate obtained by melt extrusion was used andinjection-molded in a mold having a cavity 70 mm in diameter and 3 mm inthickness and kept at a temperature of 150° C. under a pressure 1.05times as high as the minimum hold pressure under which the resincomposition was completely charged into the mold, thereby measuring thelength of flash occurred in a clearance (slit for evaluating flashlength) 20 μm in thickness and 5 mm in width, which was provided at acircumferential part of the mold, by means of a magnifying projector.

[0086] (7) Volume Resistivity:

[0087] Measured in accordance with JIS K 6911 and JIS K 7194.

Synthesis Example 1 Synthesis of PAS (A)

[0088] A polymerizer was charged with 720 kg of N-methyl-2-pyrrolidone(NMP) and 420 kg of sodium sulfide pentahydrate containing 46.21 wt. %of sodium sulfide (Na₂S). After purged with nitrogen gas, thetemperature of the reaction system was gradually raised to 200° C. withstirring to distill off 158 kg of water. At this time, 62 moles of H₂Swere volatilized off. After the dehydration step described above, thepolymerizer was charged with 371 kg of p-dichlorobenzene (hereinafterabbreviated as “pDCB”) and 189 kg of NMP to conduct a reaction at 220°C. for 4.5 hours with stirring. While continuing the stirring, 49 kg ofwater were then introduced under pressure into the polymerizer, and thecontents were heated to 255° C. to conduct a reaction for 5 hours. Aftercompletion of the reaction, the reaction mixture was cooled near to roomtemperature, and the contents were sifted through a screen of 100 meshto collect a granular polymer. The thus-collected granular polymer waswashed twice with acetone and 3 times with water, thereby obtaining awashed polymer. This washed polymer was further washed with a 0.6%aqueous solution of ammonium chloride and then washed with water. Afterdehydration, the collected granular polymer was dried at 105° C. for 3hours. The yield of the polymer [PAS (A)] thus obtained was 92%, and ithad a melt viscosity of 55 Pa·s, a pH of 6.2 and an average particlesize of about 500 μm.

Synthesis Example 2 Synthesis of PAS (B)

[0089] A polymerizer was charged with 720 kg of NMP and 420 kg of sodiumsulfide pentahydrate containing 46.21 wt. % of sodium sulfide (Na₂S).After purged with nitrogen gas, the temperature of the reaction systemwas gradually raised to 200° C. with stirring to distill off 160 kg ofwater. At this time, 62 moles of H₂S were volatilized off at the sametime.

[0090] After the dehydration step described above, the polymerizer wascharged with 364 kg of pDCB and 250 kg of NMP to conduct a reaction at220° C. for 4.5 hours with stirring. While continuing the stirring, 59kg of water were then introduced under pressure into the polymerizer,and the contents were heated to 255° C. to conduct a reaction for 5hours. After completion of the reaction, the reaction mixture was coolednear to room temperature, and the contents were sifted through a screenof 100 mesh to collect a granular polymer. The thus-collected granularpolymer was washed twice with acetone and 3 times with water, therebyobtaining a washed polymer. This washed polymer was further washed witha 3% aqueous solution of ammonium chloride and then washed with water.After dehydration, the collected granular polymer was dried at 105° C.for 3 hours. The yield of the polymer [PAS (B)] thus obtained was 89%,and it had a melt viscosity of 140 Pa·s, a pH of 6.5 and an averageparticle size of about 900 μm.

Synthesis Example 3 Synthesis of PAS (C)

[0091] A polymerizer was charged with 500 kg of NMP and 435 kg of sodiumsulfide pentahydrate containing 46.21 wt. % of sodium sulfide (Na₂S).After purged with nitrogen gas, the temperature of the reaction systemwas gradually raised to 200° C. with stirring to distill off 150 kg ofwater. At this time, 45 moles of H₂S were volatilized off at the sametime.

[0092] After the dehydration step described above, the polymerizer wascharged with 395 kg of pDCB and 320 kg of NMP to conduct a reaction at220° C. for 3.5 hours with stirring. While continuing the stirring, 35kg of water were then introduced under pressure into the polymerizer,and the contents were heated to 255° C. to conduct a reaction for 5hours. After completion of the reaction, the reaction mixture was coolednear to room temperature, and the contents were sifted through a screenof 100 mesh to collect a granular polymer. The thus-collected granularpolymer was washed twice with acetone and 3 times with water, therebyobtaining a washed polymer. This washed polymer was further washed witha 1% aqueous solution of acetic acid and then washed several times withwater. After dehydration, the collected granular polymer was dried at105° C. for 3 hours. The yield of the polymer [PAS (C)] thus obtainedwas 94%, and it had a melt viscosity of 24 Pa·s, a pH of 6.1 and anaverage particle size of about 300 μm.

Synthesis Example 4 Synthesis of Polyamide-imide (PAI)

[0093] A 20-liter reactor equipped with a stirrer, a thermometer and agas inlet tube was charged with 10 liters of NMP and then with 2 kg oftrimellitic anhydride at room temperature while introducing drynitrogen. At this point of time, the water content in the system was 45ppm. While introducing nitrogen, 1.81 kg of 2,4-tolylene diisocyanatewere immediately added, and the contents were heated from roomtemperature to 90° C. over 30 minutes. At this temperature, a reactionwas conducted for 60 minutes. Thereafter, the reaction mixture washeated further to 115° C. over 20 minutes to continue the reaction for 8hours while keeping this temperature.

[0094] After completion of the reaction, the polymer solution thusobtained was divided into halves, and 10 liters of NMP was added to eachsolution to dilute it. The each polymer solution was then added dropwiseto 40 liters of methanol stirred at high speed. Each polymer depositedwas collected by suction filtration, dispersed again in 40 liters ofmethanol and then collected by filtration. After this process wasconducted twice repeatedly, the whole collected polymer was dried underreduced pressure at 200° C. to obtain a powdery polymer. With respect tothe polymer thus obtained, absorption derived from an amide group and animide group was confirmed by the infrared absorption spectrum. Thereduced viscosity (as determined by viscosity measurement at 30° C. anda polymer concentration of 1 g/dl in dimethylformamide) was 0.22 dl/g.The glass transition temperature (as measured by a differential scanningcalorimeter) of this polymer was 323° C.

Examples 1 to 6 and Comparative Examples 1 to 7

[0095] After their corresponding respective components shown in Tables 1and 2 were uniformly dry blended in a Henschel mixer, the resultantblends were respectively fed to a twin-screw kneader extruder (PCM-45,manufactured by Ikegai Corp.) having a diameter of 45 mm and kneaded ata cylinder temperature of 260 to 340° C., thereby obtaining pellet-likeextrudates. The pellet-like extrudates thus obtained were dried at 150°C. for 6 hours and then molded at a mold temperature of 145° C. and acylinder temperature of 300 to 340° C. by an injection molding machine(IS-75, manufactured by Toshiba Machine Co., Ltd.) to form specimens fortensile test and flexural test. The formulations of the resincompositions and the measured results are shown in Tables 1 and 2. TABLE1 Comp. Comp. Comp. Ex. 1 Ex. 1 Ex. 2 Ex. 2 Ex. 3 Ex. 4 Ex. 3Formulation Resin PAS (A) (%) — — 83.3 83.3 75.0 75.0 75.0 PAS (B) (%)60.0 60.0 — — — — — PAS (D) (%) — — — — — — — PAI (%) 40.0 40.0 16.716.7 25.0 25.0 25.0 Aminoalkoxysilane (part) 0.7 — 0.8 — 0.8 0.8 —Additive Glass fiber (part) — — 66.7 66.7 66.7 66.7 66.7 Organic amidecompound (part) — — — — — 1.7 — Physical property Extrudability GoodGood Good Good Good Good Good Tensile strength MPa 89 56 190 169 187 192149 Tensile elongation % 5.60 2.20 1.35 1.15 1.44 1.34 0.99 Flexuralstrength MPa — — 235 227 233 242 217 Flexural modulus MPa 23° C. — —14050 13970 14630 14490 13970 150° C. — — — — — — — Maximum strain inbending % — — 1.78 1.67 1.68 1.75 1.59 Melt viscosity Pa's 310 280 145129 222 174 158

[0096] TABLE 2 Comp. Comp. Comp. Comp. Ex. 5 Ex. 4 Ex. 6 Ex. 5 Ex. 6 Ex.7 Formulation Resin PAS (A) (%) 58.3 58.3 50.0 50.0 — 100 PAS (B) (%) —— — — — — PAS (D) (%) — — — — 50.0 — PAI (%) 41.7 41.7 50.0 50.0 50.0 —Aminoalkoxysilane (part) 0.8 — 1.0 — — — Additive Glass fiber (part)66.7 66.7 66.7 66.7 66.7 66.7 Organic amide compound (part) — — — — — —Physical property Extrudability Good Good Good Good Good Good Tensilestrength MPa 165 140 160 115 98 185 Tensile elongation % 1.18 0.94 1.150.75 0.68 1.40 Flexural strength MPa 235 204 228 175 145 235 Flexuralmodulus MPa 23° C. 14870 14900 14200 14110 14520 14000 150° C. 7500 7500— — — 5200 Maximum strain in bending % 1.55 1.39 1.28 0.95 0.85 1.75Melt viscosity Pa's 389 353 480 420 368 140

[0097] As apparent from the experimental results shown in Tables 1 and2, the resin compositions (Examples 1 to 6) to which theaminoalkoxysilane was added are excellent in tensile strength andtensile elongation compared with their corresponding resin compositions(Comparative Examples 1 to 6) in which no aminoalkoxysilane was added.Further, the resin compositions (Examples 2 to 6) into which glass fiberwas compounded are also improved in flexural strength and maximum strainin bending. The resin composition (Example 4) into which the organicamide compound (ε-caprolactam) was compounded is further improved inmelt-flow properties (lower melt viscosity) and mechanical properties.

[0098] The resin composition (Comparative Example 6) which has a highmelt viscosity and a high pH and into which no aminoalkoxysilane wasadded is poor in extrudability and also insufficient in mechanicalproperties. In the molded products obtained by injection molding inExamples 1 to 6, the flash length was small compared with those obtainedin Comparative Examples 1 to 6.

[0099] The resin composition (Comparative Example 7) into which only PASand glass fiber were compounded, and no polyamide-imide was notcompounded was low in flexural modulus at 150° C. and insufficient instiffness at a high temperature compared with the resin composition(Example 5) in which the polyamide-imide, glass fiber andamino-alkoxysilane were compounded into the PAS. In the resincomposition according to Example 5, the flexural modulus at ordinary andhigh temperatures is equal to that of the resin composition (ComparativeExample 4) into which no aminoalkoxysilane was compounded, but thetensile strength, tensile elongation, flexural strength and maximumstrain in bending are markedly improved.

Examples 7 to 14 and Comparative Examples 8 to 15

[0100] Specimens for tensile test and flexural test were produced in thesame manner as in Examples 1 to 6 except that the formulations werechanged to their corresponding formulations shown in Tables 3 and 4. Theformulations of the resin compositions and the measured results areshown in Tables 3 and 4. TABLE 3 Comp. Comp. Comp. Comp. Ex. 7 Ex. 8 Ex.8 Ex. 9 Ex. 9 Ex. 10 Ex. 10 Ex.11 Formulation Resin PAS (A) (%) 61.061.0 — — — — — — PAS (B) (%) — — — — 60.0 60.0 — — PAS (C) (%) — — 60.060.0 — — 63.0 63.0 PAI (%) 39.0 39.0 40.0 40.0 40.0 40.0 37.0 37.0Aminoalkoxysilane (part) 0.9 — 1.1 — 0.7 — 0.9 — Additive PETS (part)0.6 0.6 0.7 0.7 — — — — Glass fiber (part) — — 70.0 70.0 — — — — Carbonfiber (part) 43.0 43.0 — — — — — — Aramid fiber (part) — — — — 11.0 11.0— — Carbon black (part) — — 3.5 3.5 — — — — PTFE (part) — — — — — — 25.025.0 Alumina (part) — — — — — — — — Silica (part) — — — — — — — —Ferrite (part) — — — — — — — — Potassium titanite (part) — — — — — — — —Physical property Tensile strength MPa 155 136 82 90 68 84 Tensileelongation % 0.47 0.5 0.3 9.8 3.2 2.9 Flexural strength (23° C.) MPa 225Failure 202 132 — — — Failure Flexural modulus (23° C.) MPa 21500 in14750 12560 — — — in Maximum strain in bending % 1.2 molding 1.4 1.1 — —— molding Melt viscosity Pa's 487 755 510 793 385 342 465 740 Volumeresistivity Ω cm 11.2 — 88 1.0E = 15 — — — —

[0101] TABLE 4 Comp. Comp. Comp. Comp. Ex. 11 Ex. 12 Ex. 12 Ex. 13 Ex.13 Ex. 14 Ex. 14 Ex.15 Formulation Resin PAS (A) (%) — — — — — — 60.060.0 PAS (B) (%) — — — — — — — — PAS (C) (%) 60.0 60.0 60.0 60.0 60.060.0 — — PAI (%) 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0Aminoalkoxysilane (part) 1.0 — 1.7 — 7.1 — 0.8 — Additive PETS (part) —— — — — — — — Glass fiber (part) — — — — — — — — Carbon fiber (part) — —— — — — — — Aramid fiber (part) — — — — — — — — Carbon black (part) — —— — — — — — PTFE (part) — — — — — — 20.0 20.0 Alumina (part) 233.0 233.0— — — — — — Silica (part) — — 67.0 67.0 — — — — Ferrite (part) — — — —567.0 567.0 — — Potassium titanite (part) — — — — — — 13.3 13.3 Physicalproperty Tensile strength MPa — — — — — — — Tensile elongation % — — — —— — — Flexural strength (23° C.) MPa 65 30 72 45 65 Failure 127 110Flexural modulus (23° C.) MPa 22090 20050 6000 6050 19800 in 7420 7500Maximum strain in bending % — — — — — molding 2.7 1.8 Melt viscosityPa's 450 480 210 190 350 300 332 310 Volume resistivity Ω cm — — — — — —— —

[0102] As apparent from the experimental results shown in Tables 3 and4, when the aminoalkoxysilane compound was added to the resincompositions into which the carbon fiber (fibrous filler), PTFE(fluorocarbon resin) and ferrite (inorganic filler) were respectivelycompounded (Examples 7, 10 and 13), the resin compositions were able tobe subjected to molding and exhibited excellent melt-flow properties andmechanical properties. On the other hand, when no aminoalkoxysilanecompound was added (Comparative Examples 8, 11 and 14), such resincompositions were unable to retain the form of molded articles, and themelt-flow properties were also poor.

[0103] When the aminoalkoxysilane compound was added to the resincompositions into which the glass fiber and carbon black, the Aramidfiber, the alumina, the silica, and the PTFE and potassium titanatewhisker were respectively compounded (Examples 8, 9, 11, 12 and 14), theflow properties and mechanical properties were improved to a greatextent compared with their corresponding resin compositions to which noaminoalkoxysilane compound was added (Comparative Examples 9, 10, 12, 13and 15). In the case of the resin compositions into which the glassfiber and carbon black were compounded, the electrical resistivity canbe greatly lowered by compounding the aminoalkoxysilane (Example 8) evenwhen only a small amount of the carbon black was compounded, as comparedwith the case where no aminoalkoxysilane was added

Comparative Example 9 Examples 15 to 23 and Comparative Examples 16 to22

[0104] Specimens for tensile test and flexural test were produced in thesame manner as in Examples 1 to 6 except that the formulations werechanged to their corresponding formulations shown in Tables 5 and 6. Theformulations of the resin compositions and the measured results areshown in Tables 5 and 6. TABLE 5 Comp. Comp. Ex. 15 Ex. 16 Ex. 16 Ex. 17Ex. 17 Ex. 18 Ex. 19 Ex.20 Formulation Resin PAS (A) (%) — — 75.0 75.058.3 58.3 58.3 58.3 PAS (B) (%) 60.0 60.0 — — — — — — PAS (C) (%) — — —— — — — — PAI (%) 40.0 40.0 25.0 25.0 41.7 41.7 41.7 41.7 SilaneCompound Epoxysilane (part) 0.7 — 0.8 — 1.2 1.2 — — Mercaptosilane(part) — — — — — — 1.2 — Isocyanatosilane (part) — — — — — — — 1.2Ureidosilane (part) — — — — — — — — Additive Glass fiber (part) — — 66.766.7 66.7 66.7 66.7 66.7 Organic amide compound (part) — — — — — 1.7 — —Physical property Tensile strength MPa 90 56 198 149 170 172 164 168Tensile elongation % 6.50 2.20 1.75 0.99 1.40 1.42 1.25 1.31 Flexuralstrength MPa — — 245 217 235 238 218 222 Flexural modulus MPa (23° C.) —— 14500 13970 14540 14900 14850 14790 (150° C.) — — — — 7500 7500 75007500 Maximum strain in bending % — — 2.15 1.59 1.70 1.75 1.58 1.62 Meltviscosity Pa's 270 280 145 158 310 260 335 340 Flash length μm — — 38 6015 14 15 15

[0105] TABLE 6 Comp. Comp. Ex. 15 Ex. 16 Ex. 16 Ex. 17 Ex. 17 Ex. 18 Ex.19 Ex.20 Formulation Resin PAS (A) (%) 58.3 58.3 — — 50.0 50.0 100.0 —PAS (B) (%) — — — — — — — — PAS (C) (%) — — 58.3 58.3 — — — 100 PAI (%)41.7 41.7 41.7 41.7 50.0 50.0 — — Silane Compound Epoxysilane (part) — —1.2 — 1.0 — — — Mercaptosilane (part) — — — — — — — — Isocyanatosilane(part) — — — — — — — — Ureidosilane (part) 1.2 — — — — — — — AdditiveGlass fiber (part) 66.7 66.7 66.7 66.7 66.7 66.7 66.7 66.7 Organic amidecompound (part) — — — — — — — — Physical property Tensile strength MPa166 133 165 125 162 115 185 175 Tensile elongation % 1.30 0.94 1.15 0.881.20 0.75 1.40 1.20 Flexural strength MPa 220 186 215 185 224 175 235220 Flexural modulus MPa (23° C.) 15000 14760 14210 14980 14280 1411014000 14500 (150° C.) 7500 7500 — — — — 5200 — Maximum strain in bending% 1.62 1.33 1.52 1.35 1.23 0.95 1.75 1.55 Melt viscosity Pa's 350 353180 230 360 420 140 80 Flash length μm 15 20 15 15 10 13 380 290

[0106] As apparent from the experimental results shown in Tables 5 and6, the resin compositions to which the silane compound having a ureido,epoxy, isocyanate or mercapto group was added (Examples 15 to 23) areexcellent in tensile strength, tensile elongation and melt-flowproperties (lower melt viscosity) compared with their correspondingresin compositions (Comparative Examples 16 to 20) to which no silanecompound was added. Further, the resin compositions (Examples 16 to 23)into which the glass fiber was compounded are also improved in flexuralstrength and maximum strain in bending. The resin composition (Example18) into which the organic amide compound (ε-caprolactam) was compoundedis low in melt viscosity and hence further improved in melt-flowproperties.

[0107] The resin compositions (Comparative Examples 21 and 22) intowhich only PAS and glass fiber were compounded, and neither thepolyamide-imide nor the silane compound having the specific functionalgroup was compounded are low in flexural modulus at 150° C.,insufficient in stiffness at a high temperature and extremely long inthe length of flash compared with the resin compositions (Examples 17 to21) in which the polyamide-imide, glass fiber and silane compound havingthe specific functional group were compounded into the PAS.

Examples 24 to 31 and Comparative Examples 23 to 30

[0108] Specimens for tensile test and flexural test were produced in thesame manner as in Examples 1 to 6 except that the formulations werechanged to their corresponding formulations shown in Tables 7 and 8. Theformulations of the resin compositions and the measured results areshown in Tables 7 and 8. TABLE 7 Comp. Comp. Comp. Comp. Ex. 24 Ex. 23Ex. 25 Ex. 24 Ex. 26 Ex. 25 Ex. 27 Ex.26 Formulation Resin PAS (A) (%)61.0 61.0 — — — — — — PAS (B) (%) — — — — 60.0 60.0 — — PAS (C) (%) — —60.0 60.0 — — 63.0 63.0 PAI (%) 39.0 39.0 40.0 40.0 40.0 40.0 37.0 37.0Epoxysilane (part) 0.9 — 1.1 — 0.7 — 0.9 — Additive PETS (part) 0.6 0.60.7 0.7 — — — — Glass fiber (part) — — 70.0 70.0 — — — — Carbon fiber(part) 43.0 43.0 — — — — — — Aramid fiber (part) — — — — 11.0 11.0 — —Carbon black (part) — — 3.5 3.5 — — — — PTFE (part) — — — — — — 25.025.0 Alumina (part) — — — — — — — — Silica (part) — — — — — — — —Ferrite (part) — — — — — — — — Potassium titanite (part) — — — — — — — —Physical property Tensile strength MPa 158 138 82 90 68 82 Tensileelongation % 0.45 0.5 0.3 8.6 3.2 2.5 Flexural strength (23° C.) MPa 230Failure 200 132 — — — Failure Flexural modulus (23° C.) MPa 22060 in14870 12560 — — — in Maximum strain in bending % 1.2 molding 1.4 1.1 — —— molding Melt viscosity Pa's 324 755 360 793 310 342 340 740 Volumeresistivity Ω cm 8.6 — 67 1.0E = 15 — — — —

[0109] TABLE 8 Comp. Comp. Comp. Comp. Ex. 11 Ex. 12 Ex. 12 Ex. 13 Ex.13 Ex. 14 Ex. 14 Ex.15 Formulation Resin PAS (A) (%) — — — — — — 60.060.0 PAS (B) (%) — — — — — — — — PAS (C) (%) 60.0 60.0 60.0 60.0 60.060.0 — — PAI (%) 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0Aminoalkoxysilane (part) 1.0 — 1.7 — 7.1 — 0.8 — Additive PETS (part) —— — — — — — — Glass fiber (part) — — — — — — — — Carbon fiber (part) — —— — — — — — Aramid fiber (part) — — — — — — — — Carbon black (part) — —— — — — — — PTFE (part) — — — — — — 20.0 20.0 Alumina (part) 233.0 233.0— — — — — — Silica (part) — — 67.0 67.0 — — — — Ferrite (part) — — — —567.0 567.0 — — Potassium titanite (part) — — — — — — 13.3 13.3 Physicalproperty Tensile strength MPa — — — — — — — Tensile elongation % — — — —— — — Flexural strength (23° C.) MPa 68 30 70 45 75 Failure 125 110Flexural modulus (23° C.) MPa 22150 22050 6120 6050 20800 in 7520 7500Maximum strain in bending % — — — — — molding 2.4 1.8 Melt viscosityPa's 390 480 142 190 255 300 272 310 Volume resistivity Ω cm — — — — — —— —

[0110] As apparent from the experimental results shown in Tables 7 and8, when the functional group-containing silane compound was added to theresin compositions into which the carbon fiber (fibrous filler), PTFE(fluorocarbon resin) and ferrite (inorganic filler) were respectivelycompounded (Examples 24, 27 and 30), the resin compositions were able tobe subjected to molding and exhibited excellent melt-flow properties andmechanical properties. On the other hand, when no functionalgroup-containing silane compound was added (Comparative Examples 23, 26and 29), such resin compositions were unable to retain the form ofmolded articles, and the melt-flow properties were also poor.

[0111] When the functional group-containing silane compound was added tothe resin compositions into which the glass fiber and carbon black, theAramid fiber, the alumina, the silica, and the PTFE and potassiumtitanate whisker were respectively compounded (Examples 25, 26, 28, 29and 31), the flow properties and mechanical properties were improved toa great extent compared with their corresponding resin compositions towhich no functional group-containing silane compound was added(Comparative Examples 24, 25, 27, 28 and 30). In the case of the resincompositions into which the glass fiber and carbon black werecompounded, the electrical resistivity can be greatly lowered bycompounding the functional group-containing silane (Example 25) evenwhen only a small amount of the carbon black was compounded, as comparedwith the case where no functional group-containing silane was added

Comparative Example 24 Industrial Applicability

[0112] According to the present invention, there are providedthermoplastic resin compositions improved in compatibility between PASand polyamide-imide and having excellent molding or forming ability,melt-flow properties and mechanical properties. The charged amount ofthe polyamide-imide to the PAS can be increased by adding the functionalgroup-containing silane compound thereto. When an epoxy group-containingsilane compound is added, the melt viscosity of the resulting resincomposition can be lowered to enhance its flow properties over a widerange of the compositional ratio of the polyamide-imide content in thePAS.

[0113] In the thermoplastic resin composition according to the presentinvention, both elastic modulus of the PAS at a high temperature andinjection moldability of the polyamide-imide are improved, and the flashlength upon injection molding is reduced. Accordingly, the resincompositions according to the present invention can be molded or formedinto sheets, films, tubes or other molded or formed products by theconventional melt processing techniques such as injection molding andextrusion. The molded or formed products thus obtained can be applied toa wide variety of field of which stiffness at a high temperature of 100°C. or higher, flame retardancy, heat resistance, chemical resistance,dimensional stability, mechanical properties, and the like are required.

[0114] The unfilled thermoplastic resin compositions and glassfiber-filled thermoplastic resin compositions are suitable for use asinsulating materials in a wide variety of fields. The carbonfiber-filled thermoplastic resin compositions are suitable for use aselectrically conductive materials or sliding materials. The Aramidfiber-, PTFE- or potassium titanate fiber-filled thermoplastic resincompositions are suitable for use as sliding materials. Thealumina-filled thermoplastic resin compositions are suitable for use asheat-conductive materials. The silica-filled thermoplastic resincompositions are suitable for use as sealing materials. Theferrite-filled thermoplastic resin compositions are suitable for use asmagnetic materials.

1. A thermoplastic resin composition comprising 100 parts by weight of aresin component containing 40 to 99 wt. % of a poly(arylene sulfide) (A)and 1 to 60 wt. % of polyamide-imide (B), and 0.01 to 10 parts by weightof a silane compound (C) containing at least one functional groupselected from the group consisting of amino, ureido, epoxy, isocyanateand mercapto groups.
 2. The thermoplastic resin composition according toclaim 1, wherein the poly(arylene sulfide) (A) has a melt viscositywithin a range of 10 to 500 Pa·s as measured at 310° C. and a shear rateof 1200/sec.
 3. The thermoplastic resin composition according to claim1, wherein the poly(arylene sulfide) (A) has a pH of at most 8.0 in a1:2 (by volume) mixed solvent of acetone and water.
 4. The thermoplasticresin composition according to claim 1, wherein the polyamide-imide (B)is a polyamide-imide obtained in accordance with a process in which anaromatic tricarboxylic acid anhydride and a diisocyanate are reactedwith each other in a solvent.
 5. The thermoplastic resin compositionaccording to claim 1, which further comprises an organic amide compound.6. The thermoplastic resin composition according to claim 1, whichfurther comprises any other thermoplastic resin.
 7. The thermoplasticresin composition according to claim 6, wherein said any otherthermoplastic resin is polytetrafluoroethylene.
 8. The thermoplasticresin composition according to claim 1, which further comprises afiller.
 9. The thermoplastic resin composition according to claim 8,wherein the filler is at least one fibrous filler.
 10. The thermoplasticresin composition according to claim 9, wherein the fibrous filler is atleast one selected from the group consisting of glass fiber, carbonfiber, Aramid fiber and potassium titanate fiber.
 11. The thermoplasticresin composition according to claim 8, wherein the filler is at leastone non-fibrous filler.
 12. The thermoplastic resin compositionaccording to claim 11, wherein the non-fibrous filler is ferrite. 13.The thermoplastic resin composition according to claim 11, wherein thenon-fibrous filler is an electrically conductive filler.
 14. Thethermoplastic resin composition according to claim 13, wherein theelectrically conductive filler is electrically conductive carbon black.15. The thermoplastic resin composition according to claim 11, whereinthe non-fibrous filler is magnetic powder.
 16. The thermoplastic resincomposition according to claim 15, wherein the magnetic powder isferrite.
 17. The thermoplastic resin composition according to claim 11,wherein the non-fibrous filler is alumina.
 18. The thermoplastic resincomposition according to claim 11, wherein the non-fibrous filler issilica.
 19. The thermoplastic resin composition according to claim 8,wherein the filler comprises at least one fibrous filler and at leastone non-fibrous filler.
 20. The thermoplastic resin compositionaccording to claim 19, wherein the filler comprises at least one fibrousfiller and electrically conductive carbon black.
 21. The thermoplasticresin composition according to claim 1, which further comprises at leastone other thermoplastic resin and at least one filler.
 22. Thethermoplastic resin composition according to claim 21, which furthercomprises polytetrafluoroethylene and potassium titanate fiber.
 23. Thethermoplastic resin composition according to claim 1, wherein thefunctional group-containing silane compound (C) is an alkoxysilanecompound or halosilane compound containing at least one functional groupselected from the group consisting of amino, ureido, epoxy, isocyanateand mercapto groups.
 24. The thermoplastic resin composition accordingto claim 23, wherein the functional group-containing alkoxy-silanecompound is a functional group-substituted alkyl. alkoxysilane compoundhaving a functional group-substituted alkyl group and an alkoxy group.25. The thermoplastic resin composition according to claim 24, whereinthe functional group-substituted alkyl group in the functionalgroup-substituted alkyl. alkoxysilane compound has 1 to 4 carbon atoms,and the alkoxy group has 1 to 4 carbon atoms.
 26. The thermoplasticresin composition according to claim 25, wherein the functionalgroup-substituted alkyl-alkoxysilane compound is a γ-aminopropyl.trialkoxysilane compound, γ-glycidoxypropyl. trialkoxysilane,γ-mercaptopropyl-trialkoxysilane, γ-isocyanatopropyl trialkoxysilane orγ-ureidopropyl-trialkoxysilane.
 27. The thermoplastic resin compositionaccording to claim 23, wherein the epoxy group-containing silanecompound is at least one selected from the group consisting ofγ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropyldimethylmethoxysilane,γ-glycidoxypropyl-triethoxysilane,γ-glycidoxypropylmethyldiethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane andβ-(3,4-epoxycyclohexyl)ethyltriethoxysilane.